Compounds and organic electronic devices

ABSTRACT

The present invention relates to certain fluorenes, to the use of the compounds in an electronic device, and to an electronic device comprising at least one of these compounds. The present invention furthermore relates to a process for the preparation of the compounds and to a formulation and composition comprising one or more of the compounds.

The present invention relates to novel organic compounds, to the use ofthe compounds in an electronic device, and to an electronic devicecomprising at least one of the compounds. The present inventionfurthermore relates to a process for the preparation of the compoundsand to compositions and formulations comprising at least one of thecompounds.

The development of functional compounds for use in electronic devices iscurrently the subject of intensive research. The aim here is, inparticular, the development of compounds with which improved propertiesof electroluminescent devices in one or more relevant points can beachieved, such as, for example, power efficiency, lifetime or colourcoordinates of the emitted light.

In accordance with the present invention, the term electronic device istaken to mean, inter alia, organic integrated circuits (OICs), organicfield-effect transistors (OFETs), organic thin-film transistors (OTFTs),organic light-emitting transistors (OLETs), organic solar cells (OSCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (OFQDs), organic light-emitting electrochemical cells (OLECs),organic laser diodes (O-lasers) and organic electroluminescent devices(OLEDs).

Of particular interest is the provision of compounds for use in thelast-mentioned electronic devices called OLEDs. The general structureand the functional principle of OLEDs are well known to the personskilled in the art and are described, inter alia, in U.S. Pat. Nos.4,539,507, 5,151,629, EP 0676461 and WO 1998/27136.

Further improvements are still necessary with respect to the performancedata of OLEDs, in particular with a view to broad commercial use, forexample in display devices or as light sources. Of particular importancein this connection are the lifetime, the efficiency and the operatingvoltage of the OLEDs and the colour values achieved. In addition, it isdesirable, for use as functional materials in electronic devices, forthe compounds to have high thermal stability and a high glass-transitiontemperature and to be sublimable without decomposition.

In this connection, there is, in particular, a need for alternativehole-transport materials. In hole-transport materials in accordance withthe prior art, the voltage generally increases with increasing layerthickness of the hole-transport layer. In practice, a greater layerthickness of the hole-transport layer would frequently be desirable, butthis often has the consequence of a higher operating voltage and worseperformance data. In this connection, there is a need for novelhole-transport materials which have high charge-carrier mobility,enabling thicker hole-transport layers to be achieved with an onlyslight increase in the operating voltage.

The prior art describes the use of various fluorenes as charge-transportmaterial in electronic and electroluminescent devices.

WO 2011/055493 discloses secondary amines which are polysubstituted byfluorenes in position 3.

JP 2008-34701 and WO 2007/072952 disclose fluorenes which aresubstituted in position 4 by an amine group, where the amine groupitself again contains a number of fluorenes.

WO 2010/110553 discloses fluorenes which are substituted by amine groupsin position 2, 3 or 4, where the amine groups contain carbazole groups.

JP 05303221 discloses fluorenes which may be substituted in position 2or 4 by an amine group. The compounds containing the amine group inposition 4 of the fluorene contain phenyl radicals. The compounds areemployed as photoreceptors.

In spite of the compounds already known, there continues to be a needfor novel hole-transport and hole-injection materials for use in OLEDs.In particular, there is a need for materials with which theabove-mentioned, highly desired improvements in the performance data andproperties of OLEDs can be achieved.

There is likewise a need for novel matrix materials for use in OLEDs andin other electronic devices. In particular, there is a need for matrixmaterials for phosphorescent dopants and for matrix materials formixed-matrix systems, which preferably result in good efficiency, a longlifetime and a low operating voltage of the electronic devices.

The present invention is thus based on the object of providingelectroluminescent devices and compounds which are suitable for use inelectroluminescent devices, such as, for example, in fluorescent orphosphorescent OLEDs, and which can be employed, in particular, ashole-transport materials and/or as hole-injection materials in ahole-transport or excton-blocking layer or as matrix material in anemitting layer.

As part of the present invention, it has been found, surprisingly, thatcompounds of the formula (1) indicated below are highly suitable for theabove-mentioned uses in electronic and in particular inelectroluminescent devices.

The invention thus relates to a compound of the general formula (1)

where the following applies to the symbols and indices used:

-   R¹ is on each occurrence, identically or differently, preferably    identically, H, D, F, C, Br, I, C(═O)R⁴, CN, Si(R⁴)₃, NO₂,    P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴, a straight-chain alkyl, alkoxy or    thioalkyl group having 1 to 20 C atoms or a branched or cyclic    alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an    alkenyl or alkynyl group having 2 to 20 C atoms, where the    above-mentioned groups may each be substituted by one or more    radicals R⁴ and where one or more CH₂ groups in the above-mentioned    groups may be replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, C═S,    C═NR⁴, —C(═O)O—, —C(═O)NR⁴—, P(═O)(R⁴), —O—, —S—, SO or SO₂ and    where one or more H atoms in the above-mentioned groups may be    replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 6 to 30 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁴, or an    aryloxy group having 5 to 60 aromatic ring atoms, which may be    substituted by one or more radicals R⁴, or an aralkyl group having 5    to 60 aromatic ring atoms, which may in each case be substituted by    one or more radicals R⁴, where the two radicals R¹ may be linked to    one another and may form a ring, so that a spiro compound forms in    position 9 of the fluorene, where spirobifluorenes are excluded;-   R², R³ are on each occurrence, identically or differently,    preferably identically, H, D, F, C, Br, I, C(═O)R⁴, CN, Si(R⁴)₃,    NO₂, P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴, N(R⁴)₂, a straight-chain alkyl,    alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or    cyclic alkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an    alkenyl or alkynyl group having 2 to 20 C atoms, where the    above-mentioned groups may each be substituted by one or more    radicals R⁴ and where one or more CH₂ groups in the above-mentioned    groups may be replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, C═S,    C═NR⁴, —C(═O)O—, —C(═O)NR⁴—, P(═O)(R⁴), —O—, —S—, SO or SO₂ and    where one or more H atoms in the above-mentioned groups may be    replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 6 to 30 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁴, or an    aryloxy group having 5 to 60 aromatic ring atoms, which may be    substituted by one or more radicals R⁴, or an aralkyl group having 5    to 60 aromatic ring atoms, which may in each case be substituted by    one or more radicals R⁴, where two or more radicals R² or two or    more radicals R³ may be linked to one another and may form a ring;-   R⁴ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R⁵, CN, Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵,    N(R⁵)₂, a straight-chain alkyl, alkoxy or thioalkyl group having 1    to 20 C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl    group having 3 to 20 C atoms or an alkenyl or alkynyl group having 2    to 20 C atoms, where the above-mentioned groups may each be    substituted by one or more radicals R⁵ and where one or more CH₂    groups in the above-mentioned groups may be replaced by —R⁵C═CR⁵—,    —C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—, P(═O)(R⁵),    —O—, —S—, SO or SO₂ and where one or more H atoms in the    above-mentioned groups may be replaced by D, F, Cl, Br, I, CN or    NO₂, or an aromatic or heteroaromatic ring system having 5 to 30    aromatic ring atoms, which may in each case be substituted by one or    more radicals R⁵, or an aryloxy or heteroaryloxy group having 5 to    30 aromatic ring atoms, which may be substituted by one or more    radicals R⁵;-   R⁵ is selected from the group consisting of H, D, F, an aliphatic    hydrocarbon radical having 1 to 20 C atoms or an aromatic or    heteroaromatic ring system having 5 to 30 C atoms, in which one or    more H atoms may be replaced by D or F, where two or more adjacent    substituents R⁵ may form a mono- or polycyclic, aliphatic ring    system with one another;-   p, q, r    -   are 0 or 1, where p+q+r=1, preferably p=1 or r=1 and very        preferably p=1;-   Z^(a) ₀, Z^(b) ₀, Z^(c) ₀    -   are, identically or differently on each occurrence, equal to R³;-   Z^(a) ₁, Z^(b) ₁, Z^(c) ₁ are equal to

-   B′ is a single bond, an aryl group having 6 to 30 ring atoms or a    mono- or bicyclic heteroaryl group having 5 to 30 ring atoms, each    of which may be substituted by one or more radicals R⁴,    -   preferably a single bond or a phenylene, biphenylene,        terphenylene, naphthylene, pyridinylene, pyrimidinylene,        pyrazinylene, pyridazinylene, triazinylene, dibenzofuranylene or        dibenzothiophenylene group, each of which may be substituted by        one or more radicals R⁴,    -   very preferably a single bond or a phenylene, biphenylene,        terphenylene, naphthylene, dibenzofuranylene or        dibenzothiophenylene group, each of which may be substituted by        one or more radicals R⁴,    -   B′ is very particularly preferably a single bond or a phenylene        group, which may be substituted by one or more radicals R⁴,    -   B′ is especially preferably a single bond,    -   where, if B′ is a single bond, the nitrogen atom is bonded        directly to the fluorene;-   Ar¹, Ar²    -   are on each occurrence, identically or differently, an aromatic        or heteroaromatic radical having 10 to 60 aromatic ring atoms,        which may be substituted by one or more radicals R⁶, which are        identical to or different from one another, where the two groups        Ar¹ or Ar² each contain at least two or more aromatic or        heteroaromatic rings,    -   where two of the aromatic or heteroaromatic rings in Ar¹ or in        Ar² may be condensed, but are preferably in uncondensed form,    -   and where two of the aromatic or heteroaromatic rings in Ar¹ may        be bridged by a divalent group —O—, —S— or —Si(R⁶)₂—, where        bridging via —O— or —Si(R⁶)₂— is preferred, or two of the        aromatic or heteroaromatic rings in Ar² may be bridged by a        divalent group —O—, —S— or —Si(R⁶)₂—, where bridging via —O— or        —Si(R⁶)₂— is preferred, where unbridged rings are very        preferred,    -   and where an aromatic or heteroaromatic ring from Ar¹ may be        bridged to an aromatic or heteroaromatic ring from Ar² by a        divalent group —O—, —S—, —Si(R⁶)₂—, —NR⁶— or —C(R⁶)₂—, where        unbridged groups Ar¹ and Ar² are preferred;-   R⁶ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, C(═O)R⁵, CN, Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, a    straight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 20 C atoms or an alkenyl or alkynyl group having 2 to 20    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R⁵ and where one or more CH₂ groups in the    above-mentioned groups may be replaced by —R⁵C═CR⁵—, —C≡C—, Si(R⁵)₂,    C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—, P(═O)(R⁵), —O—, —S—, SO or    SO₂ and where one or more H atoms in the above-mentioned groups may    be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or    heteroaromatic ring system having 5 to 30 aromatic ring atoms, which    may in each case be substituted by one or more radicals R⁵, or an    aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms,    which may be substituted by one or more radicals R⁵;    with the proviso that Z^(a) ₁, Z^(b) ₁ and Z^(c) ₁ in the compound    of the formula (1) contain no fluorene or carbazole groups and with    the proviso that the compound of the formula (1) contains no    condensed aromatic or heteroaromatic ring systems having more than    10 ring atoms, where it is preferred for the compound of the    formula (1) to contain no condensed aromatic or heteroaromatic ring    systems.

It is furthermore preferred in the sense of the present invention forthe compound of the formula (1) to contain no further fluorenes orcarbazoles.

The numbering on the fluorene here is defined as follows:

An aryl group in the sense of this invention contains 6 to 60 aromaticring atoms; a heteroaryl group in the sense of this invention contains 5to 60 aromatic ring atoms, at least one of which is a heteroatom. Theheteroatoms are preferably selected from N, O and S. This represents thebasic definition. If other preferences are indicated in the descriptionof the present invention, for example with respect to the number ofaromatic ring atoms or the heteroatoms present, these apply.

An aryl group or heteroaryl group here is taken to mean either a simplearomatic ring, i.e. benzene, or a simple heteroaromatic ring, forexample pyridine, pyrimidine or thiophene, or a condensed (annellated)aromatic or heteroaromatic polycycle, for example naphthalene,phenanthrene, quinoline or carbazole. A condensed (annellated) aromaticor heteroaromatic polycycle in the sense of the present applicationconsists of two or more simple aromatic or heteroaromatic ringscondensed with one another.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals and which may be linked to the aromatic orheteroaromatic ring system via any desired positions, is taken to mean,in particular, groups derived from benzene, naphthalene, anthracene,phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene,benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene,furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzo-pyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aryloxy group in accordance with the definition of the presentinvention is taken to mean an aryl group, as defined above, which isbonded via an oxygen atom. An analogous definition applies toheteroaryloxy groups.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a non-aromatic unit (preferably less than 10% of the atomsother than H), such as, for example, an sp³-hybridised C, Si, N or Oatom, an sp²-hybridised C or N atom or an sp-hybridised C atom. Thus,for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene,triarylamine, diaryl ether, stilbene, etc., are also intended to betaken to be aromatic ring systems in the sense of this invention, as aresystems in which two or more aryl groups are connected, for example, bya linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.Furthermore, systems in which two or more aryl or heteroaryl groups arelinked to one another via single bonds are also taken to be aromatic orheteroaromatic ring systems in the sense of this invention, such as, forexample, systems such as biphenyl, terphenyl or diphenyltriazine.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may in each case also be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, quaterphenyl, fluorene,spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene,cis- or trans-indenofluorene, truxene, isotruxene, spiro-truxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, indolocarbazole, indenocarbazole,pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzo-pyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole, or combinations ofthese groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals, ispreferably taken to mean the radicals methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl,cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl,cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl,pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl,pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,cyclo-heptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl,pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl group having 1 to40 C atoms is preferably taken to mean methoxy, trifluoromethoxy,ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy,n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy,n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy,pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio,n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio,t-butylthio, n-pentylthio, s-pentylthio, n-hexylthio, cyclohexylthio,n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio,2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio,2,2,2-trifluoroethylthio, ethenylthio, propenylthio, butenylthio,pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio,heptenylthio, cycloheptenylthio, octenylthio, cyclooctenylthio,ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio,heptynylthio or octynylthio.

It is preferred for B′ in the compound of the formula (1) to be a singlebond.

It is furthermore preferred for B′ in the compound of the formula (1) tobe an o-phenylene, m-phenylene or p-phenylene group, a 1,4-naphthylene,2,4-naphthylene, 1,5-naphthylene or 2,5-naphthylene group, a3,7-dibenzofuranylene group or a 3,7-dibenzothiophenylene group, whereit is very preferred for B′ to be an o-phenylene, m-phenylene orp-phenylene group and it is very particularly preferred for B′ to be ap-phenylene group, where the groups may be substituted by one or moreradicals R⁴, which may be identical or different on each occurrence,where it is preferred for the groups to be unsubstituted.

Preference is given in the sense of the present invention to a compoundof the general formula (2)

where the above definitions apply to the indices and symbols used.

Preference is furthermore given to a compound of the general formula (1)or (2), characterised in that R¹ is on each occurrence, identically ordifferently, preferably identically, a straight-chain alkyl or alkoxygroup having 1 to 20 C atoms or a branched or cyclic alkyl or alkoxygroup having 3 to 20 C atoms, where the above-mentioned groups may eachbe substituted by one or more radicals R⁴, or an aromatic orheteroaromatic ring system having 6 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁴, or an aryloxygroup having 5 to 60 aromatic ring atoms, which may be substituted byone or more radicals R⁴, or an aralkyl group having 5 to 60 aromaticring atoms, which may in each case be substituted by one or moreradicals R⁴, where the two radicals R¹ may be linked to one another andmay form a ring, so that a spiro compound forms in position 9 of thefluorene, where spirobifluorenes are excluded.

Great preference is furthermore given to a compound of the generalformula (1) or (2), characterised in that R¹ is on each occurrence,identically or differently, preferably identically, a straight-chainalkyl group having 1 to 20 C atoms or a branched or cyclic alkyl grouphaving 3 to 20 C atoms, where the above-mentioned groups may each besubstituted by one or more radicals R⁴, or an aromatic or heteroaromaticring system having 6 to 30 aromatic ring atoms, which may in each casebe substituted by one or more radicals R⁴, where the two radicals R¹ maybe linked to one another and may form a ring, so that a spiro compoundforms in position 9 of the fluorene, where spirobifluorenes areexcluded.

Very particular preference is furthermore given to a compound of thegeneral formula (1) or (2), characterised in that R¹ is on eachoccurrence, identically, a straight-chain alkyl group having 1 to 20 Catoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴, where it is especially preferred for R¹ to be a methyl,ethyl, n-/i-propyl or n-/i-/t-butyl group.

Finally, very particular preference is furthermore given to a compoundof the general formula (1) or (2), characterised in that R¹ is on eachoccurrence an aromatic or heteroaromatic ring system having 6 to 30aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁴, where the ring system is especially preferablyselected from the group consisting of a phenyl, biphenyl, terphenyl orpyridyl group.

Preference is furthermore given to a compound of the general formula (1)or (2), characterised in that R² is selected on each occurrence,identically or differently, preferably identically, from H, D, F, Cl,Br, I, N(R⁵)₂, a straight-chain alkyl or alkoxy group having 1 to 20 Catoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 Catoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁴ and where one or more H atoms in the above-mentioned groups may bereplaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromaticring system having 6 to 30 aromatic ring atoms, which may in each casebe substituted by one or more radicals R⁴, or an aryloxy group having 5to 60 aromatic ring atoms, which may be substituted by one or moreradicals R⁴, or an aralkyl group having 5 to 60 aromatic ring atoms,which may in each case be substituted by one or more radicals R⁴, wheretwo or more radicals R² may be linked to one another and may form aring.

Great preference is furthermore given to a compound of the generalformula (1) or (2), characterised in that R² is selected on eachoccurrence, identically or differently, preferably identically, from H,D, F, Cl, Br, I, N(R⁵)₂, a straight-chain alkyl group having 1 to 20 Catoms or a branched or cyclic alkyl group having 3 to 20 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴ and where one or more H atoms in the above-mentioned groupsmay be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system having 6 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁴.

In a very particularly preferred embodiment, the present inventionrelates to a compound of the general formula (1) which is characterisedin that R² is equal to H.

In a further very particularly preferred embodiment, the presentinvention relates to a compound of the general formula (1) which ischaracterised in that R² is a straight-chain alkyl group having 1 to 20C atoms or a branched or cyclic alkyl group having 3 to 20 C atoms.

In still a further very particularly preferred embodiment, the presentinvention relates to a compound of the general formula (1) which ischaracterised in that R² represents an aromatic or heteroaromatic ringsystem having 6 to 30 aromatic ring atoms.

Preference is furthermore given to a compound of the general formula (1)or (2), characterised in that R³ is selected on each occurrence,identically or differently, from H, D, F, Cl, Br, I, N(R⁵)₂, astraight-chain alkyl or alkoxy group having 1 to 20 C atoms or abranched or cyclic alkyl or alkoxy group having 3 to 20 C atoms, wherethe above-mentioned groups may each be substituted by one or moreradicals R⁴ and where one or more H atoms in the above-mentioned groupsmay be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system having 6 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁴, or an aryloxygroup having 5 to 60 aromatic ring atoms, which may be substituted byone or more radicals R⁴, or an aralkyl group having 5 to 60 aromaticring atoms, which may in each case be substituted by one or moreradicals R⁴, where two or more radicals R³ may be linked to one anotherand may form a ring.

Preference is given in the sense of the present invention to a compoundof the general formula (1a)

where the above definitions apply to the symbols and indices used and tothe preferred embodiments described herein.

Great preference is given in the sense of the present invention to acompound of the general formula (2a)

where the above definitions apply to the symbols and indices used and tothe preferred embodiments described herein.

In a preferred embodiment, the present invention relates to a compoundof the general formula (3)

where the above definitions apply to the symbols and indices used.

In a furthermore preferred embodiment, the present invention relates toa compound of the general formula (4)

where the above definitions apply to the symbols and indices used.

If the amine containing the groups Ar¹ and Ar² is located in position 3of the fluorene, it is particularly preferred for the group Ar¹ or thegroup Ar² to have no bridging via oxygen, since the use of thesecompounds in OLEDs results in particularly advantageous performancedata.

In a furthermore preferred embodiment, the present invention relates toa compound of the general formula (5)

where the above definitions apply to the symbols and indices used.

In a very preferred embodiment, the present invention relates to acompound of the general formula (6)

where the above definitions apply to the symbols and indices used.

In a furthermore very preferred embodiment, the present inventionrelates to a compound of the general formula (7)

where the above definitions apply to the symbols and indices used.

In a furthermore very preferred embodiment, the present inventionrelates to a compound of the general formula (8)

where the above definitions apply to the symbols and indices used.

In a very particularly preferred embodiment, the present inventionrelates to a compound of the general formula (9)

where the above definitions apply to the symbols and indices used.

In a furthermore very particularly preferred embodiment, the presentinvention relates to a compound of the general formula (10)

where the above definitions apply to the symbols and indices used.

In a furthermore very particularly preferred embodiment, the presentinvention relates to a compound of the general formula (11)

where the above definitions apply to the symbols and indices used.

In an especially preferred embodiment, the present invention relates toa compound of the general formula (12)

where the above definitions apply to the symbols and indices used.

In a furthermore especially preferred embodiment, the present inventionrelates to a compound of the general formula (13)

where the above definitions apply to the symbols and indices used.

In a furthermore especially preferred embodiment, the present inventionrelates to a compound of the general formula (14)

where the above definitions apply to the symbols and indices used.

Preference is furthermore given to a compound of the formulae (1) to(14) indicated above in which B′ is selected from the groups of theformulae (15) to (36), where these groups may also be substituted by oneor more radicals R⁴, which are independent of one another, and where R⁴is defined as indicated above.

where the dashed lines denote the linking positions.

Great preference is given to a compound of the formulae (1) to (14)indicated above in which B′ is selected from the groups of the formulae(15) to (36), where these groups are unsubstituted.

Very particular preference is given to a compound of the formulae (1) to(14) indicated above in which B′ corresponds to the formula (15), wherethis group is unsubstituted.

Especial preference is given to a compound of the formulae (1) to (14),characterised in that B′ is a single bond, where the nitrogen atom isthen bonded directly to the fluorene via a single bond.

Ar¹ and Ar² are preferably selected, identically or differently on eachoccurrence, from a phenyl-pyridyl, phenyl-naphthyl, biphenyl, terphenylor quaterphenyl group, which may be substituted by one or more radicalsR⁶, which may be identical to or different from one another, where twoof the aromatic or heteroaromatic rings in Ar¹ may be bridged by adivalent group —O—, —S— or —Si(R⁶)₂— or two of the aromatic orheteroaromatic rings in Ar² may be bridged by a divalent group —O—, —S—or —Si(R⁶)₂—, where unbridged rings are preferred, and where an aromaticor heteroaromatic ring from Ar¹ may be bridged to an aromatic orheteroaromatic ring from Ar² by a divalent group —O—, —S—, —Si(R⁶)₂—,—NR⁶— or —C(R⁶)₂—, where unbridged groups Ar¹ and Ar² are preferred.

In a very preferred embodiment of the present invention, Ar¹ and Ar² areselected, identically or differently on each occurrence, from thefollowing groups of the formulae (37) to (116), which may be substitutedby one or more radicals R⁶.

where the dashed line denotes the linking position to the nitrogen atom.

In a preferred embodiment, the present invention relates to a compoundof the general formula (6), where the following applies to the symbolsused:

-   R¹    -   is on each occurrence, identically or differently, preferably        identically, a straight-chain alkyl group having 1 to 20 C atoms        or a branched or cyclic alkyl group having 3 to 20 C atoms,        where the above-mentioned groups may each be substituted by one        or more radicals R⁴, or an aromatic or heteroaromatic ring        system having 6 to 30 aromatic ring atoms, which may in each        case be substituted by one or more radicals R⁴, where the two        radicals R¹ may be linked to one another and may form a ring, so        that a spiro compound forms in position 9 of the fluorene, where        spirobifluorenes are excluded;-   R²    -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;-   R³    -   is equal to H, D, F, C, Br, I, a straight-chain alkyl or alkoxy        group having 1 to 20 C atoms or a branched or cyclic alkyl or        alkoxy group having 3 to 20 C atoms, where the above-mentioned        groups may each be substituted by one or more radicals R⁴ and        where one or more H atoms in the above-mentioned groups may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or        heteroaromatic ring system having 6 to 30 aromatic ring atoms,        which may in each case be substituted by one or more radicals        R⁴, or an aryloxy group having 5 to 60 aromatic ring atoms,        which may be substituted by one or more radicals R⁴, or an        aralkyl group having 5 to 60 aromatic ring atoms, which may in        each case be substituted by one or more radicals R⁴, where two        or more radicals R³ may be linked to one another and may form a        ring;-   B′    -   is selected from H or the groups of the formulae (15) to (36),        where these groups may also be substituted by one or more        radicals R⁴, which are independent of one another, and where R⁴        is defined as indicated above;-   Ar¹, Ar²    -   are, identically or differently on each occurrence, a        phenyl-pyridyl, phenyl-naphthyl, biphenyl, terphenyl or        quaterphenyl group, which may be substituted by one or more        radicals R⁶, which may be identical to or different from one        another, where two of the aromatic or heteroaromatic rings in        Ar¹ may be bridged by a divalent group —O—, —S— or —Si(R⁶)₂— or        two of the aromatic or heteroaromatic rings in Ar² may be        bridged by a divalent group —O—, —S— or —Si(R⁶)₂—, where        unbridged rings are preferred, and where an aromatic or        heteroaromatic ring from Ar¹ may be bridged to an aromatic or        heteroaromatic ring from Ar² by a divalent group —O—, —S—,        —Si(R⁶)₂—, —NR⁶— or —C(R⁶)₂—, where unbridged groups Ar¹ and Ar²        are preferred.

In a very preferred embodiment, the present invention relates to acompound of the general formula (6), where the following applies to thesymbols used:

R¹

-   -   is on each occurrence, identically or differently, preferably        identically, a straight-chain alkyl group having 1 to 20 C        atoms, where the said group may be substituted by one or more        radicals R⁴, or an aromatic or heteroaromatic ring system having        6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where the two radicals        R¹ may be linked to one another and may form a ring, so that a        spiro compound forms in position 9 of the fluorene, where        spirobifluorenes are excluded;

R²

-   -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;

R³

-   -   is equal to H or an aromatic or heteroaromatic ring system        having 6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where R³ is especially        preferably equal to H;

B′

-   -   is a single bond;        Ar¹, Ar²    -   are, identically or differently on each occurrence, a biphenyl,        terphenyl or quaterphenyl group, which may be substituted by one        or more radicals R⁶, which may be identical to or different from        one another, where the rings in Ar¹ and Ar² are unbridged, Ar¹        and Ar² are especially preferably a biphenyl group, which may be        substituted by one or more radicals R⁶, which may be identical        to or different from one another.

In a very particularly preferred embodiment, the present inventionrelates to a compound of the general formula (6), where the followingapplies to the symbols used:

R¹

-   -   is identical on each occurrence and is a straight-chain alkyl        group having 1 to 5 C atoms, preferably a methyl group or ethyl        group, where the said group may be substituted by one or more        radicals R⁴, or represents a phenyl, biphenyl or pyridyl group,        each of which may be substituted by one or more radicals R⁴,        where the two alkyl groups R¹ may be linked to one another and        may form a ring, so that a spiro compound forms in position 9 of        the fluorene, where spirobifluorenes are excluded;

R²

-   -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;

R³

-   -   is equal to H or an aromatic or heteroaromatic ring system        having 6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where R³ is especially        preferably equal to H;

B′

-   -   is a single bond;        Ar¹, Ar²    -   are, identically or differently on each occurrence, a biphenyl,        terphenyl or quaterphenyl group, which may be substituted by one        or more radicals R⁶, which may be identical to or different from        one another, where the rings in Ar¹ and Ar² are unbridged, Ar¹        and Ar² are especially preferably a biphenyl group, which may be        substituted by one or more radicals R⁶, which may be identical        to or different from one another.

In a further preferred embodiment, the present invention relates to acompound of the general formula (8), where the following applies to thesymbols used:

R¹

-   -   is on each occurrence, identically or differently, preferably        identically, a straight-chain alkyl group having 1 to 20 C atoms        or a branched or cyclic alkyl group having 3 to 20 C atoms,        where the above-mentioned groups may each be substituted by one        or more radicals R⁴, or an aromatic or heteroaromatic ring        system having 6 to 30 aromatic ring atoms, which may in each        case be substituted by one or more radicals R⁴, where the two        radicals R¹ may be linked to one another and may form a ring, so        that a spiro compound forms in position 9 of the fluorene, where        spirobifluorenes are excluded;

R²

-   -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;

R³

-   -   is equal to H, D, F, C, Br, I, a straight-chain alkyl or alkoxy        group having 1 to 20 C atoms or a branched or cyclic alkyl or        alkoxy group having 3 to 20 C atoms, where the above-mentioned        groups may each be substituted by one or more radicals R⁴ and        where one or more H atoms in the above-mentioned groups may be        replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or        heteroaromatic ring system having 6 to 30 aromatic ring atoms,        which may in each case be substituted by one or more radicals        R⁴, or an aryloxy group having 5 to 60 aromatic ring atoms,        which may be substituted by one or more radicals R⁴, or an        aralkyl group having 5 to 60 aromatic ring atoms, which may in        each case be substituted by one or more radicals R⁴, where two        or more radicals R³ may be linked to one another and may form a        ring;

B′

-   -   is selected from H or the groups of the formulae (15) to (36),        where these groups may also be substituted by one or more        radicals R⁴, which are independent of one another, and where R⁴        is defined as indicated above;        Ar¹, Ar²    -   are, identically or differently on each occurrence, a        phenyl-pyridyl, phenyl-naphthyl, biphenyl, terphenyl or        quaterphenyl group, which may be substituted by one or more        radicals R⁶, which may be identical to or different from one        another, where two of the aromatic or heteroaromatic rings in        Ar¹ may be bridged by a divalent group —O—, —S— or —Si(R⁶)₂— or        two of the aromatic or heteroaromatic rings in Ar² may be        bridged by a divalent group —O—, —S— or —Si(R⁶)₂—, where        unbridged rings are preferred, and where an aromatic or        heteroaromatic ring from Ar¹ may be bridged to an aromatic or        heteroaromatic ring from Ar² by a divalent group —O—, —S—,        —Si(R⁶)₂—, —NR⁶— or —C(R⁶)₂—, where unbridged groups Ar¹ and Ar²        are preferred.

In a very preferred embodiment, the present invention relates to acompound of the general formula (8), where the following applies to thesymbols used:

R¹

-   -   is on each occurrence, identically or differently, preferably        identically, a straight-chain alkyl group having 1 to 20 C        atoms, where the said group may be substituted by one or more        radicals R⁴, or an aromatic or heteroaromatic ring system having        6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where the two radicals        R¹ may be linked to one another and may form a ring, so that a        spiro compound forms in position 9 of the fluorene, where        spirobifluorenes are excluded;

R²

-   -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;

R³

-   -   is equal to H or an aromatic or heteroaromatic ring system        having 6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where R³ is especially        preferably equal to H;

B′

-   -   is a single bond;        Ar¹, Ar²    -   are, identically or differently on each occurrence, a biphenyl,        terphenyl or quaterphenyl group, which may be substituted by one        or more radicals R⁶, which may be identical to or different from        one another, where the rings in Ar¹ and Ar² are unbridged, Ar¹        and Ar² are especially preferably a biphenyl group, which may be        substituted by one or more radicals R⁶, which may be identical        to or different from one another.

In a very particularly preferred embodiment, the present inventionrelates to a compound of the general formula (8) where the followingapplies to the symbols used:

R¹

-   -   is identical on each occurrence and is a straight-chain alkyl        group having 1 to 5 C atoms, preferably a methyl group or ethyl        group, where the said group may be substituted by one or more        radicals R⁴, or represents a phenyl, biphenyl or pyridyl group,        each of which may be substituted by one or more radicals R⁴,        where the two alkyl groups R¹ may be linked to one another and        may form a ring, so that a spiro compound forms in position 9 of        the fluorene, where spirobifluorenes are excluded;

R²

-   -   is equal to H, a straight-chain alkyl group having 1 to 20 C        atoms or a branched or cyclic alkyl group having 3 to 20 C        atoms, where the groups may be substituted by one or more        radicals R⁴, an aromatic or heteroaromatic ring system having 6        to 30 aromatic ring atoms, which may be substituted by one or        more radicals R⁴;

R³

-   -   is equal to H or an aromatic or heteroaromatic ring system        having 6 to 30 aromatic ring atoms, which may in each case be        substituted by one or more radicals R⁴, where R³ is especially        preferably equal to H;

B′

-   -   is a single bond;        Ar¹, Ar²    -   are, identically or differently on each occurrence, a biphenyl,        terphenyl or quaterphenyl group, which may be substituted by one        or more radicals R⁶, which may be identical to or different from        one another, where the rings in Ar¹ and Ar² are unbridged, Ar¹        and Ar² are especially preferably a biphenyl group, which may be        substituted by one or more radicals R⁶, which may be identical        to or different from one another.

In an especially preferred embodiment, the present invention relates tocompounds of the general formula (1), characterised in that they aremonoamine compounds.

The synthesis of the compounds according to the invention can be carriedout by processes which are known to the person skilled in the art fromthe prior art. The preparation can be carried out, for example, by meansof halogenation, Buchwald coupling and Suzuki coupling.

The following reaction scheme shows a preferred synthetic route for thepreparation of the compounds of the formula (1) according to theinvention. For the synthesis of the compounds according to theinvention, the fluorene compound A is reacted with an amine B of theformula Ar¹—NH—Ar² in a Buchwald coupling,

where the above definitions apply to the symbols and indices used andwhereX^(a) ₀, X^(b) ₀, X^(c) ₀ are, identically or differently on eachoccurrence, equal to R³, andX^(a) ₁, X^(b) ₁, X^(c) ₁ are equal to —B′—Y, where Y is a leavinggroup, for example halogen.

Another preferred synthetic route for the preparation of the compoundsaccording to the invention is depicted in the following reaction scheme.The synthetic route comprises two coupling reactions: firstly, thefluorene compound A is reacted with an amine B of the formula Ar¹—NH₂ ina first Buchwald coupling. Finally, a second Buchwald coupling iscarried out with a compound D, for example a bromoaryl compound.

where Y is again a leaving group, for example halogen;and whereXX^(a) ₀, XX^(b) ₀, XX^(c) ₀ are, identically or differently on eachoccurrence, equal to R³, andXX^(a) ₁, XX^(b) ₁, XX^(c) ₁ are equal to —B′—NH—Ar¹.

The following scheme shows a further preferred synthetic route for thepreparation of compounds according to the invention. For this purpose,benzochromenones E serve as the starting point. The addition reaction ofan organometallic reagent, for example a Grignard or organolithiumreagent, and subsequent acid-catalysed cyclisation of the intermediatealcoholate results in the corresponding 4-hydroxyfluorenes F. Thehydroxyl group is subsequently converted into a leaving group Y or —B′—Y(═X^(a) ₁), for example into a triflate (TfO) or a halide (preferably Bror CI), and further into the compounds according to the invention by amethod familiar to the person skilled in the art (C—C coupling, such asSuzuki, Negishi, Yamamoto, Grignard-Cross, Stille, Heck coupling, etc.,C—N coupling, such as Buchwald coupling), where a Buchwald coupling or aSuzuki coupling is preferred. In the case of X^(a) ₁, only Y is ofcourse the leaving group.

where the indices used are defined as indicated above, and B stands fora boron atom.

This enables the preparation of fluorenes which have the amine in thepreferred position 4.

Fluorenes according to the invention which have the amine in position 1of the fluorene can be prepared entirely analogously thereto.

Boronic acid esters containing the groups R which are employed for theSuzuki coupling are well known to the person skilled in the art.

Synthetic routes for starting compounds A, B, C, D, E and F which areemployed in the synthesis of the compounds according to the inventionare familiar to the person skilled in the art. Furthermore, someexplicit synthetic processes are described in detail in the workingexamples.

Preferred coupling reactions for the preparation of the compound of thegeneral formula (1) are Buchwald couplings.

Preferred compounds according to the invention are shown by way ofexample in the following table.

The compounds of the formula (1) described above may be substituted byreactive leaving groups, such as bromine, iodine, chlorine, boronic acidor boronic acid ester. These can be used as monomers for the productionof corresponding oligomers, dendrimers or polymers. Suitable reactiveleaving groups are, for example, bromine, iodine, chlorine, boronicacids, boronic acid esters, amines, alkenyl or alkynyl groups having aterminal C—C double bond or C—C triple bond, oxiranes, oxetanes, groupswhich undergo a cycloaddition, for example a 1,3-dipolar cycloaddition,such as, for example, dienes or azides, carboxylic acid derivatives,alcohols and silanes.

The invention therefore furthermore relates to oligomers, polymers ordendrimers containing one or more compounds of the formula (1), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired possible positions in formula (1). Depending on the linkingof the compound of the formula (1), the compound is a constituent of aside chain of the oligomer or polymer or a constituent of the mainchain. An oligomer in the sense of this invention is taken to mean acompound which is built up from at least three monomer units. A polymerin the sense of the invention is taken to mean a compound which is builtup from at least ten monomer units. The polymers, oligomers ordendrimers according to the invention may be conjugated, partiallyconjugated or non-conjugated. The oligomers or polymers according to theinvention may be linear, branched or dendritic. In the structures linkedin a linear manner, the units of the formula (1) may be linked directlyto one another or they may be linked to one another via a divalentgroup, for example via a substituted or unsubstituted alkylene group,via a heteroatom or via a divalent aromatic or heteroaromatic group. Inbranched and dendritic structures, for example, three or more units ofthe formula (1) may be linked via a trivalent or polyvalent group, forexample via a trivalent or polyvalent aromatic or heteroaromatic group,to form a branched or dendritic oligomer or polymer.

The same preferences as described above for compounds of the formula (1)apply to the recurring units of the formula (1) in oligomers, dendrimersand polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 2000/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 2006/061181), para-phenylenes (for example in accordance with WO1992/18552), carbazoles (for example in accordance with WO 2004/070772or WO 2004/113468), thiophenes (for example in accordance with EP1028136), dihydrophenanthrenes (for example in accordance with WO2005/014689 or WO 2007/006383), cis- and trans-indenofluorenes (forexample in accordance with WO 2004/041901 or WO 2004/113412), ketones(for example in accordance with WO 2005/040302), phenanthrenes (forexample in accordance with WO 2005/104264 or WO 2007/017066) or also aplurality of these units. The polymers, oligomers and dendrimers usuallyalso contain further units, for example emitting (fluorescent orphosphorescent) units, such as, for example, vinyltriarylamines (forexample in accordance with WO 2007/068325) or phosphorescent metalcomplexes (for example in accordance with WO 2006/003000), and/orcharge-transport units, in particular those based on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (1) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;(B) YAMAMOTO polymerisation;(C) STILLE polymerisation; and(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 2002/067343 A1 and WO 2005/026144 A1.

The compounds, polymers, oligomers and dendrimers according to theinvention can be employed as compositions with other organicallyfunctional materials which are used in electronic devices. A largenumber of possible organically functional materials is known to theperson skilled in the art from the prior art. The present inventiontherefore also relates to a composition comprising one or more compoundsof the formula (1) according to the invention and at least one polymer,oligomer or dendrimer according to the invention and at least onefurther organically functional material selected from the groupconsisting of fluorescent emitters, phosphorescent emitters, hostmaterials, matrix materials, electron-transport materials,electron-injection materials, hole-conductor materials, hole-injectionmaterials, electron-blocking materials and hole-blocking materials.

For the processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,formulations of the compounds according to the invention are necessary.These formulations can be, for example, solutions, dispersions ormini-emulsions. It may be preferred to use mixtures of two or moresolvents for this purpose.

Suitable and preferred solvents are, for example, toluene, anisole, o-,m- or p-xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin,veratrol, THF, methyl-THF, THP, chlorobenzene, dioxane or mixtures ofthese solvents.

The invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or mini-emulsion, comprising at leastone compound of the formula (1) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (1), and at leastone solvent, preferably an organic solvent. The way in which solutionsof this type can be prepared is known to the person skilled in the artand is described, for example, in WO 2002/072714, WO 2003/019694 and theliterature cited therein.

The compounds according to the invention are suitable for use inelectronic devices, in particular in organic electroluminescent devices(for example OLEDs or OLECs). Depending on the substitution, thecompounds are employed in different functions and layers.

The present invention therefore furthermore relates to the use of thecompound of the formula (1) in electronic devices and to electronicdevices themselves which comprise one or more compounds of the formula(1). The electronic devices here are preferably selected from the groupconsisting of organic integrated circuits (OICs), organic field-effecttransistors (OFETs), organic thin-film transistors (OTFTs), organiclight-emitting transistors (OLETs), organic solar cells (OSCs), organicoptical detectors, organic photoreceptors, organic field-quench devices(OFQDs), organic light-emitting electrochemical cells (OLECs), organiclaser diodes (0-lasers) and particularly preferably organicelectroluminescent devices (OLEDs and OLECs).

The invention relates, as already stated above, to electronic devicescomprising at least one compound of the formula (1). The electronicdevices here are preferably selected from the devices mentioned above.Particular preference is given to organic electroluminescent devices(OLEDs) comprising anode, cathode and at least one emitting layer,characterised in that at least one organic layer, which may be anemitting layer, a hole-transport layer or another layer, comprises atleast one compound of the formula (1).

Apart from the cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, interlayers, charge-generation layers (IDMC2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K.Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL DeviceHaving Charge Generation Layer) and/or organic or in-organic p/njunctions. However, it should be pointed out that each of these layersdoes not necessarily have to be present and the choice of layers isalways dependent on the compounds used and in particular also on whetherthe electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device according to the invention maycomprise a plurality of emitting layers. These emission layers in thiscase particularly preferably have in total a plurality of emissionmaxima between 380 nm and 750 nm, resulting overall in white emission,i.e. various emitting compounds which are able to fluoresce orphosphoresce and which emit blue or yellow or orange or red light areused in the emitting layers. Particular preference is given tothree-layer systems, i.e. systems having three emitting layers, wherethe three layers exhibit blue, green and orange or red emission (for thebasic structure see, for example, WO 2005/011013). The compoundsaccording to the invention may be present in such devices in ahole-transport layer, an emitting layer and/or in another layer. Itshould be noted that, for the generation of white light, an emittercompound used individually which emits in a broad wavelength range mayalso be suitable instead of a plurality of emitter compounds emitting ina colour.

It is preferred in accordance with the invention for the compound of theformula (1) to be employed in an electroluminescent device comprisingone or more phosphorescent dopants. The compound can be used in variouslayers here, preferably in an hole-transport layer, a hole-injectionlayer or in an emitting layer. However, the compound of the formula (1)can also be employed in accordance with the invention in an electronicdevice comprising one or more fluorescent dopants.

The term phosphorescent dopants typically encompasses compounds in whichthe light emission takes place by a spin-forbidden transition, forexample a transition from an excited triplet state or a state having arelatively high spin quantum number, for example a quintet state.

Suitable phosphorescent dopants (=triplet emitters) are, in particular,compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particularly preferably greater than 56 and less than 80. Thephosphorescent emitters used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium,platinum or copper complexes are regarded as phosphorescent compounds.

Examples of the emitters described above are revealed by theapplications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 2005/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able to employ further phosphorescent complexes withoutinventive step in combination with the compounds of the formula (1) inorganic electroluminescent devices.

Explicit examples of suitable phosphorescent emitter compounds arefurthermore revealed by the following table.

In a preferred embodiment of the invention, the compounds of the generalformula (1) are employed as hole-transport material. The compounds arethen preferably employed in a hole-transport layer and/or in ahole-injection layer. A hole-injection layer in the sense of thisinvention is a layer which is directly adjacent to the anode. Ahole-transport layer in the sense of this invention is a layer which islocated between the hole-injection layer and the emission layer. Thehole-transport layer may be directly adjacent to the emission layer. Ifthe compounds of the formula (1) are used as hole-transport material oras hole-injection material, it may be preferred for them to be dopedwith electron-acceptor compounds (p-doping), for example with F₄-TCNQ,F₆-TNAP or compounds as described in EP 1476881 or EP 1596445. In afurther preferred embodiment of the invention, a compound of the formula(1) is used as hole-transport material in combination with ahexaazatriphenylene derivative, as described in US 2007/0092755. Thehexaazatriphenylene derivative here is particularly preferably employedin a separate layer.

If the compounds of the general formula (1) are employed ashole-transport material in a hole-transport layer, the compound may beemployed as pure material, i.e. in a proportion of 100%, in thehole-transport layer, or it may be employed in combination with one ormore further compounds in the hole-transport layer.

In a further embodiment of the present invention, the compounds of thegeneral formula (1) are employed as emitting materials. For thispurpose, the compounds are preferably employed in an emission layer.Besides at least one of the compounds of the general formula (1), theemission layer furthermore comprises at least one host material. Theperson skilled in the art will be able to make a selection from theknown host materials without difficulties and without being inventive.

In a further embodiment of the present invention, the compounds of thegeneral formula (1) are employed as matrix material in combination withone or more dopants, preferably phosphorescent dopants.

A dopant in a system comprising a matrix material and a dopant is takento mean the component whose proportion in the mixture is the smaller.Correspondingly, a matrix material is taken to mean the component whoseproportion in the mixture is the greater in a system comprising a matrixmaterial and a dopant.

The proportion of the matrix material in the emitting layer is in thiscase between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5%by vol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of dopants. In this case too,the dopants are generally the materials whose proportion in the systemis the smaller and the matrix materials are the materials whoseproportion in the system is the greater. In individual cases, however,the proportion of an individual matrix material in the system may besmaller than the proportion of an individual dopant.

In a further preferred embodiment of the invention, the compounds of thegeneral formula (1) are used as a component of mixed-matrix systems. Themixed-matrix systems preferably comprise two or three different matrixmaterials, particularly preferably two different matrix materials. Oneof the two materials here is preferably a material havinghole-transporting properties and the other material is a material havingelectron-transporting properties. However, the desiredelectron-transporting and hole-transporting properties of themixed-matrix components may also be combined principally or completelyin a single mixed-matrix components, where the further mixed-matrixcomponent(s) fulfil other functions. The two different matrix materialshere may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1,particularly preferably 1:10 to 1:1 and very particularly preferably 1:4to 1:1. Mixed-matrix systems are preferably employed in phosphorescentorganic electroluminescent devices. More precise information onmixed-matrix systems is given, inter alia, in the application WO2010/108579.

The mixed-matrix systems may comprise one or more dopants, preferablyone or more phosphorescent dopants. In general, mixed-matrix systems arepreferably employed in phosphorescent organic electroluminescentdevices.

Particularly suitable matrix materials which can be used as matrixcomponents of a mixed-matrix system in combination with the compoundsaccording to the invention are selected from the preferred matrixmaterials for phosphorescent dopants indicated below or the preferredmatrix materials for fluorescent dopants, depending on what type ofdopant is employed in the mixed-matrix system.

Preferred phosphorescent dopants for use in mixed-matrix systems are thephosphorescent dopants shown in the above table.

The materials preferably employed in the relevant functions in thedevices according to the invention are indicated below.

Preferred fluorescent dopants are selected from the class of thearylamines. An arylamine or aromatic amine in the sense of thisinvention is taken to mean a compound which contains three substitutedor unsubstituted aromatic or heteroaromatic ring systems bonded directlyto the nitrogen. At least one of these aromatic or heteroaromatic ringsystems is preferably a condensed ring system, particularly preferablyhaving at least 14 aromatic ring atoms. Preferred examples thereof arearomatic anthracenamines, aromatic anthracenediamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position.

Suitable matrix materials, preferably for fluorescent dopants, besidesthe compounds according to the invention, are materials from variousclasses of substance. Preferred matrix materials are selected from theclasses of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 2004/081017), thehole-conducting compounds (for example in accordance with WO2004/058911), the electron-conducting compounds, in particular ketones,phosphine oxides, sulfoxides, etc. (for example in accordance with WO2005/084081 and WO 2005/084082), the atropisomers (for example inaccordance with WO 2006/048268), the boronic acid derivatives (forexample in accordance with WO 2006/117052) or the benzanthracenes (forexample in accordance with WO 2008/145239). Particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising naphthalene, anthracene, benzanthracene and/or pyrene oratropisomers of these compounds, the oligoarylenevinylenes, the ketones,the phosphine oxides and the sulfoxides. Very particularly preferredmatrix materials are selected from the classes of the oligoarylenes,comprising anthracene, benzanthracene, benzophenanthrene and/or pyreneor atropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

Preferred matrix materials for phosphorescent dopants, besides thecompounds according to the invention, are aromatic amines, in particulartriarylamines, for example in accordance with US 2005/0069729, carbazolederivatives (for example CBP, N,N-biscarbazolylbiphenyl) or compounds inaccordance with WO 2005/039246, US 2005/0069729, JP 2004/288381, EP1205527 or WO 2008/086851, bridged carbazole derivatives, for example inaccordance with WO 2011/088877 and WO 2011/128017, indenocarbazolederivatives, for example in accordance with WO 2010/136109 and WO2011/000455, azacarbazole derivatives, for example in accordance with EP1617710, EP 1617711, EP 1731584, JP 2005/347160, indolocarbazolederivatives, for example in accordance with WO 2007/063754 or WO2008/056746, ketones, for example in accordance with WO 2004/093207 orWO 2010/006680, phosphine oxides, sulfoxides and sulfones, for examplein accordance with WO 2005/003253, oligophenylenes, bipolar matrixmaterials, for example in accordance with WO 2007/137725, silanes, forexample in accordance with WO 2005/111172, azaboroles or boronic esters,for example in accordance with WO 2006/117052, triazine derivatives, forexample in accordance with WO 2010/015306, WO 2007/063754 or WO2008/056746, zinc complexes, for example in accordance with EP 652273 orWO 2009/062578, aluminium complexes, for example BAlq, diazasilole andtetraazasilole derivatives, for example in accordance with WO2010/054729, diazaphosphole derivatives, for example in accordance withWO 2010/054730, and aluminium complexes, for example BAlq.

Suitable charge-transport materials, as can be used in thehole-injection or hole-transport layer or in the electron-transportlayer of the organic electroluminescent device according to theinvention, are, for example, the compounds disclosed in Y. Shirota etal., Chem. Rev. 2007, 107(4), 953-1010, or other materials as areemployed in these layers in accordance with the prior art.

The cathode of the organic electroluminescent device preferablycomprises metals having a low work function, metal alloys ormultilayered structures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further metals which have a relatively highwork function, such as, for example, Ag or Al, can also be used inaddition to the said metals, in which case combinations of the metals,such as, for example, Ca/Ag, Mg/Ag or Ag/Ag, are generally used. It mayalso be preferred to introduce a thin interlayer of a material having ahigh dielectric constant between a metallic cathode and the organicsemiconductor. Suitable for this purpose are, for example, alkali metalfluorides or alkaline-earth metal fluorides, but also the correspondingoxides or carbonates (for example LiF, Li₂, BaF₂, MgO, NaF, CsF, Cs₂CO₃,etc.). Furthermore, lithium quinolinate (LiQ) can be used for thispurpose. The layer thickness of this layer is preferably between 0.5 and5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiOx, Al/PtOx) mayalso be preferred. For some applications, at least one of the electrodesmust be transparent or partially transparent in order to facilitateeither irradiation of the organic material (organic solar cells) or thecoupling-out of light (OLEDs, O-lasers). Preferred anode materials hereare conductive mixed metal oxides. Particular preference is given toindium tin oxide (ITO) or indium zinc oxide (IZO).

Preference is furthermore given to conductive, doped organic materials,in particular conductive, doped polymers.

The device is appropriately (depending on the application) structured,pro-vided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare coated by means of a sublimation process, in which the materials areapplied by vapour deposition in vacuum sublimation units at an initialpressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are coated by means of the OVPD(organic vapour phase deposition) process or with the aid of carrier-gassublimation, in which the materials are applied at a pressure of between10⁻⁵ mbar and 1 bar. A special case of this process is the OVJP (organicvapour jet printing) process, in which the materials are applieddirectly through a nozzle and are thus structured (for example M. S.Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (1) arenecessary for this purpose. High solubility can be achieved throughsuitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

In accordance with the invention, the electronic devices comprising oneor more compounds of the general formula (1) can be employed indisplays, as light sources in lighting applications and as light sourcesin medical and/or cosmetic applications (for example light therapy).

Devices comprising the compounds of the general formula (1) can beemployed in a very versatile manner. Thus, for example,electroluminescent devices comprising one or more compounds of thegeneral formula (1) can be employed in displays for televisions, mobiletelephones, computers and cameras. However, the devices can also be usedin lighting applications.

Furthermore, electroluminescent devices, for example in OLEDs or OLECs,comprising at least one of the compounds of the general formula (1) canbe used for phototherapy in medicine or cosmetics. Thus, a large numberof diseases (psoriasis, atopic dermatitis, inflammation, acne, skincancer, etc.) can be treated or skin wrinkling, skin reddening and skinageing can be prevented or reduced. Furthermore, the light-emittingdevices can be utilised in order to keep drinks, meals or foods fresh orin order to sterilise equipment (for example medical equipment).

The compounds according to the invention and the organicelectroluminescent devices according to the invention are distinguishedby the following surprising advantages over the prior art:

-   1. The compounds according to the invention are very highly suitable    for use in a hole-transport layer or a hole-injection layer in    electronic devices, such as, for example, in organic    electroluminescent devices, in particular owing to their high hole    mobility.-   2. The compounds according to the invention have a relatively low    sublimation temperature, high temperature stability and high    oxidation stability and a high glass-transition temperature, which    is advantageous both for the processability, for example from    solution or from the gas phase, and also for use in electronic    devices.-   3. The use of the compounds according to the invention in electronic    devices, in particular employed as hole-transport or hole-injection    material, results in high efficiencies, low operating voltages and    long lifetimes.

It should be pointed out that variations of the embodiments described inthe present invention fall within the scope of this invention. Eachfeature disclosed in the present invention can, unless explicitlyexcluded, be replaced by alternative features which serve the same, anequivalent or a similar purpose. Thus, each feature disclosed in thepresent invention is, unless stated otherwise, to be regarded as anexample of a generic series or as an equivalent or similar feature.

All features of the present invention can be combined with one anotherin any way, unless certain features and/or steps are mutually exclusive.This applies in particular to preferred features of the presentinvention. Equally, features of non-essential combinations can be usedseparately (and not in combination).

It should furthermore be pointed out that many of the features, and inparticular those of the preferred embodiments of the present invention,are themselves inventive and should not merely be regarded as part ofthe embodiments of the present invention. For these features,independent protection may be sought in addition or as an alternative toeach invention currently claimed.

The teaching on technical action disclosed with the present inventioncan be abstracted and combined with other examples.

The invention is explained in greater detail by the following examples,without wishing to restrict it thereby.

EXAMPLES Materials

Materials HIL1, HIL2 (EP 0676461), H1 (WO 2008/145239), H2 (WO2010/136109), ETM1 (WO 2005/053055), SEB1 (WO 2008/006449), LiQ, Irpyand NPB are well known to the person skilled in the art from the priorart. Compounds HTMV1 to HTMV6 are comparative compounds, which can beprepared analogously to the process described in Example 1. Compounds(1-1), (1-4), (1-7) (5-1), (4-1), (1-12), (1-13), (1-14), (1-15), (6-3),(6-2), (6-1), (6-4), (6-5), (8-1), (7-2), (7-1), (9-2), (2-7), (2-8) and(1-17) are in accordance with the invention.

Example 1 Synthesis of the compoundbisbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)amine (1-1) and compounds(1-2) to (1-12)

4-Bromo-9,9-diphenyl-9H-fluorene

37 g (152 mmol) of 2,2′-dibromobiphenyl are dissolved in 300 ml of driedTHF in a flask which has been dried by heating. The reaction mixture iscooled to −78° C. 75 ml of a 15% solution of n-BuLi in hexane (119 mmol)are slowly added dropwise at this temperature (duration: about 1 hour).The batch is stirred at −70° C. for a further 1 h. 21.8 g ofbenzophenone (119 mmol) are subsequently dissolved in 100 ml of THF andadded dropwise at −70° C. When the addition is complete, the reactionmixture is slowly warmed to room temperature, quenched using NH₄Cl andsubsequently evaporated in a rotary evaporator. 510 ml of acetic acidare carefully added to the evaporated solution, and 100 ml of fuming HClare subsequently added. The batch is heated to 75° C. and kept at thistemperature for 4 h. A white solid precipitates out during this time.The batch is then cooled to room temperature, the precipitated solid isfiltered off with suction and rinsed with methanol. The residue is driedat 40° C. in vacuo. The yield is 33.2 g (83 mmol) (70% of theory).

The following brominated compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

78%

70%

82%

85%

80%

85%

77%

Bisbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-4-yl)amine (1-1)

17 g of bisbiphenyl-4-ylamine (53 mmol) and 23.1 g of4-bromo-9,9-diphenyl-9H-fluorene (58 mmol) are dissolved in 500 ml oftoluene: the solution is degassed and saturated with N₂. 5.3 ml (5.3mmol) of a 1 M tri-tert-butylphosphine solution and 0.6 g (2.65 mmol) ofpalladium(II) acetate are then added. 12.7 g of sodium tert-butoxide(132.23 mmol) are subsequently added. The reaction mixture is heated atthe boil for 3 h under a protective atmosphere. The mixture issubsequently partitioned between toluene and water, and the organicphase is washed three times with water, dried over Na₂SO₄ and evaporatedin a rotary evaporator. After filtration of the crude product throughsilica gel with toluene, the residue which remains is recrystallisedfrom heptane/toluene and finally sublimed in a high vacuum.

The purity is 99.9%. The yield is 29 g (87% of theory).

The following compounds (1-2) to (1-17) are prepared analogously

Starting Starting material 1 material 2 Product Yield

78% (1-2)

83% (1-3)

92% (1-4)

88% (1-5)

77% (1-6)

75% (1-7)

80% (1-8)

77% (1-9)

71% (1-10)

70% (1-11)

75% 2 equiv. (1-12)

77% 2 equiv. (1-13)

75% (1-14)

85% (1-15)

79% (1-16)

72% (1-17)

Example 2 Synthesis of the compoundbiphenyl-3-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)amine (2-1) andcompounds (2-2) to (2-10)

3-Bromo-9,9-dimethyl-9H-fluorene

29.5 g (120 mmol) of 3-bromo-9H-fluorene (Tetrahedron Letters, 51, 37,4894-4897; 2010) are dissolved in 220 ml of dried DMSO in a flask whichhas been dried by heating. 34.7 g (361 mmol) of NaO^(t)Bu are added atroom temperature. The suspension is brought to an internal temperatureof 65° C. A solution of 22.5 ml (361 mmol) of iodomethane in DMSO (50ml) is added dropwise at this temperature at such a rate that theinternal temperature does not exceed 65° C. (duration: about 30 min).The batch is kept at an internal temperature of 65° C. for a further 30min., and subsequently poured into 400 ml of an ice-cold aqueous NH₄OHsolution (1/1, v/v) and stirred for about 20 min. The precipitated solidis filtered off with suction and washed successively with about 200 mlof H₂O and methanol. Yield: 31 g (114 mmol) (95% of theory).

The following brominated compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

H₃C—I

78%

85%

Biphenyl-3-ylbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-3-yl)amine (2-1)

30 g of biphenyl-3-ylbiphenyl-4-ylamine (93.4 mmol) and 25.5 g of3-bromo-9,9-dimethyl-9H-fluorene (93.4 mmol) are dissolved in 600 ml oftoluene: the solution is degassed and saturated with N₂. 3.2 g (3.73mmol) of tri-tert-butylphosphine and 0.42 g (1.87 mmol) of palladium(II)acetate are then added. 13.9 g of sodium tert-butoxide (140 mmol) aresubsequently added. The reaction mixture is heated at the boil for 5 hunder a protective atmosphere. The mixture is subsequently partitionedbetween toluene and water, and the organic phase is washed three timeswith water, dried over Na₂SO₄ and evaporated in a rotary evaporator.After filtration of the crude product through silica gel with toluene,the residue which remains is recrystallised from heptane/toluene andfinally sublimed in a high vacuum. The purity is 99.9%. The yield is37.8 g (79% of theory).

The following compounds (2-2) to (2-10) are prepared analogously:

Starting Starting material 1 material 2 Product Yield

78% (2-2)

82% (2-3)

80% (2-4)

92% (2-5)

75% (2-6)

67% (2-7)

73% (2-8)

70% (2-9)

66% (2-10)

Example 3 Synthesis of the compoundbiphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (3-1) andcompounds (3-2) to (3-5)

3-Bromo-9,9-diphenyl-9H-fluorene

50 g (193 mmol) of 3-bromo-9H-fluorenone (Tetrahedron, 51, 7, 2039-54;1995) are dissolved in 500 ml of dried THF in a flask which has beendried by heating. The clear solution is cooled to −10° C., and 70.7 ml(212 mmol) of a 3 M phenylmagnesium bromide solution are then added. Thereaction mixture is slowly warmed to room temperature and then quenchedusing NH₄C (500 ml). The mixture is subsequently partitioned betweenethyl acetate and water, and the organic phase is washed three timeswith water, dried over Na₂SO₄ and evaporated in a rotary evaporator. Thecrude product is recrystallised from heptane/toluene. 400 ml of benzeneare added to the residue. The batch is heated to 50° C., and 18.6 ml oftrifluoromethanesulfonic acid are subsequently added dropwise. After 30min., the reaction mixture is cooled to room temperature and poured into1 l of water. The mixture is partitioned between toluene and water, andthe organic phase is washed three times with water, dried over Na₂SO₄and evaporated in a rotary evaporator. Filtration of the crude productthrough silica gel with heptane/ethyl acetate 1:1 gives 55.6 g (135mmol) (70% of theory).

The following brominated compounds are prepared analogously:

Starting Starting Starting material 1 material 2 material 3 ProductYield

75%

65%

Biphenyl-2-ylbiphenyl-4-yl-(9,9-diphenyl-9H-fluoren-3-yl)amine (3-1)

12 g of biphenyl-2-ylbiphenyl-4-ylamine (37 mmol), 16.3 g of3-bromo-9,9-diphenyl-9H-fluorene (41 mmol) are dissolved in 360 ml oftoluene: the solution is degassed and saturated with N₂. 3.7 ml (3.7mmol) of a 1 M solution of tri-tert-butylphosphine and 0.42 g (1.87mmol) of palladium(II) acetate are then added. 9.0 g of sodiumtert-butoxide (93.3 mmol) are subsequently added. The reaction mixtureis heated at the boil for 3 h under a protective atmosphere. The mixtureis subsequently partitioned between toluene and water, and the organicphase is washed three times with water, dried over Na₂SO₄ and evaporatedin a rotary evaporator. After filtration of the crude product throughsilica gel with toluene, the residue which remains is recrystallisedfrom heptane/toluene and finally sublimed in a high vacuum. The purityis 99.9%. The yield is 20 g (85% of theory).

The following compounds (3-2) to (3-5) are prepared analogously:

Starting Starting material 1 material 2 Product Yield

78% (3-2)

80% (3-3)

85% (3-4)

80% (3-5)

Example 4 Synthesis of the compoundbisbiphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (4-1) andcompounds (4-2) to (4-7)

4-(4-Chlorophenyl)-9,9-diphenyl-9H-fluorene

7.9 g (50 mmol) of 4-chlorobenzeneboronic acid, 20 g (50 mmol) of4-bromo-9,9-diphenyl-9H-fluorene and 55 ml of an aqueous 2 M NaHCO₃solution (111 mmol) are suspended in 400 ml of dimethoxyethane. 1.45 g(1.26 mmol) of tetrakis(triphenylphosphine)palladium(0) are added tothis suspension. The reaction mixture is heated under reflux for 16 h.After cooling, the organic phase is separated off, filtered throughsilica gel, washed three times with 300 ml of water and subsequentlyevaporated to dryness. Filtration of the crude product through silicagel with heptane/ethyl acetate (20:1) gives 18.4 g (85%) of4-(4-chlorophenyl)-9,9-diphenyl-9H-fluorene.

The following chlorinated compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

79%

70%

72%

Bisbiphenyl-4-yl-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine (4-1)

13.60 g of bisbiphenyl-4-ylamine (43 mmol) and 18.2 g of4-chloro-9,9-diphenyl-9H-fluorene (43 mmol) are dissolved in 400 ml oftoluene: the solution is degassed and saturated with N₂. 1.04 g (2.55mmol) of S-Phos and 1.94 g (2.1307 mmol) of palladium(II) dba are thenadded. 10 g of sodium tert-butoxide (106 mmol) are subsequently added.The reaction mixture is heated at the boil for 3 h under a protectiveatmosphere. The mixture is subsequently partitioned between toluene andwater, and the organic phase is washed three times with water, driedover Na₂SO₄ and evaporated in a rotary evaporator.

After filtration of the crude product through silica gel with toluene,the residue which remains is recrystallised from heptane/toluene andfinally sublimed in a high vacuum. The purity is 99.9%. The yield is 23g (77% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

78%

70%

75%

88%

73%

73%

Example 5 Synthesis of the compoundbisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine(5-1) and compounds (5-2) to (5-5)

Bisbiphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amine

15.0 g (29 mmol) of bisbiphenyl-4-yl-(9,9-dimethyl-9H-fluoren-4-yl)amineare dissolved in 150 ml of acetonitrile, and 5.2 g (29 mmol) ofN-bromo-succinimide are added in portions at room temperature. When thereaction is complete, water and ethyl acetate are added, and the organicphase is separated off, dried and evaporated. The crude product issubsequently washed by stirring a number of times with hot MeOH/heptane(1:1). Yield: 13.5 g (80%) of the product.

The following brominated compounds are prepared analogously:

Starting material 1 Product Yield

85%

81%

Bisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine(5-1)

6.3 g (22 mmol) of N-phenylcarbazol-3-ylboronic acid and 13 g (22 mmol)of bisbiphenyl-4-yl-(1-bromo-9,9-dimethyl-9H-fluoren-4-yl)amine aresuspended in 200 ml of dimethoxyethane and 30 ml of 2 M Na₂CO₃ solution.0.6 g (2.0 mmol) of tetrakis(triphenylphosphine)palladium is added tothis suspension. The reaction mixture is heated under reflux for 16 h.After cooling, the reaction mixture is diluted with ethyl acetate, andthe organic phase is separated off, washed three times with 100 ml ofwater and subsequently evaporated to dryness. Filtration of the crudeproduct through silica gel with heptane/ethyl acetate (20:1) gives 15 g(90%) ofbisbiphenyl-4-yl-[9,9-dimethyl-1-(9-phenyl-9H-carbazol-3-yl)-9H-fluoren-4-yl]amine(5-1).

Compounds (5-2) to (5-5) are prepared analogously:

Starting Starting material 1 material 2 Product Yield

85%

81%

88%

85%

Example 6 Synthesis of the compoundbiphenyl-4-yl-(4-dibenzofuran-4-yl-phenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine(6-1) and compounds (6-2) to (6-5)

Biphenyl-4-yl-(4-chlorophenyl)-(4-dibenzofuran-4-ylphenyl)amine

30.0 g of biphenyl-4-yl-(4-dibenzofuran-4-ylphenyl)amine (CAS:955959-89-4) (73 mmol) and 17.4 g of 1-chloro-2-iodobenzene (73 mmol)are dissolved in 460 ml of toluene: the solution is degassed andsaturated with N₂. 2.9 ml (2.9 mmol) of a 1 M tri-tert-butylphosphinesolution and 0.33 g (1.46 mmol) of palladium(II) acetate are then added.10.5 g of sodium tert-butoxide (109 mmol) are subsequently added. Thereaction mixture is heated at the boil for 3 h under a protectiveatmosphere. The mixture is subsequently partitioned between toluene andwater, and the organic phase is washed three times with water, driedover Na₂SO₄ and evaporated in a rotary evaporator. After filtration ofthe crude product through silica gel with toluene, the residue whichremains is recrystallised from heptane/toluene and finally sublimed in ahigh vacuum. The purity is 99.9%. The yield is 30 g (80% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

83%

80%

79%

Biphenyl-4-yl-(4-dibenzofuran-4-ylphenyl)-[4-(9,9-diphenyl-9H-fluoren-4-yl)phenyl]amine(6-1)

20.0 g (45 mmol) of pinacolyl (9,9-diphenyl-9H-fluoren-4-yl)boronate,23.5 g (45 mmol) ofbiphenyl-4-yl-(4-chlorophenyl)-(4-dibenzofuran-4-yl-phenyl)-amine aresuspended in 400 ml of dioxane and 13.7 g of caesium fluoride (90 mmol).4.0 g (5.4 mmol) of bis(tricyclohexylphosphine)palladium dichloride areadded to this suspension, and the reaction mixture is heated underreflux for 18 h. After cooling, the organic phase is separated off,filtered through silica gel, washed three times with 80 ml of water andsubsequently evaporated to dryness. After filtration of the crudeproduct through silica gel with toluene, the residue which remains isrecrystallised from heptane/toluene and finally sublimed in a highvacuum. The purity is 99.9%. The yield is 25 g (80% of theory).

The following compounds (6-2) to (6-5) are prepared analogously:

Starting Starting material 1 material 2 Product Yield

65%

69%

75%

65%

Example 7 Synthesis of the compoundbisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine(7-1) and compounds (7-2) to (7-5)

8-Dibenzofuran-4-ylbenzo[c]chromen-6-one

30.0 g (142 mmol) of dibenzofuran-4-boronic acid, 32 g (142 mmol) of8-chlorobenzo[c]chromen-6-one (CAS: 742058-81-7) and 43 g of caesiumfluoride (283 mmol) are suspended in 800 ml of dioxane. 12.5 g (17 mmol)of bis(tricyclohexylphosphine)palladium dichloride are added to thissuspension, and the reaction mixture is heated under reflux for 18 h.After cooling, the organic phase is separated off, filtered throughsilica gel, washed three times with 100 ml of water and subsequentlyevaporated to dryness. After filtration of the crude product throughsilica gel with toluene, the residue which remains is recrystallisedfrom heptane/toluene. The yield is 45 g (88% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

84%

90%

85%

76%

7-Dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol

25.4 g (70 mmol) of 8-dibenzofuran-4-ylbenzo[c]chromen-6-one aredissolved in 340 ml of dried THF in a flask which has been dried byheating. The solution is saturated with N₂. The clear solution is cooledto −10° C., and 70 ml (210 mmol) of a 3 M phenylmagnesium bromidesolution are then added. The reaction mixture is slowly warmed to roomtemperature and then quenched using acetic anhydride (70 mmol). Themixture is subsequently partitioned between ethyl acetate and water, andthe organic phase is washed three times with water, dried over Na₂SO₄and evaporated in a rotary evaporator. 310 ml of acetic acid arecarefully added to the evaporated solution, and 70 ml of fuming HCl aresubsequently added. The batch is heated to 75° C. and kept at thistemperature for 4 h. A white solid precipitates out during this time.The batch is then cooled to room temperature, and the precipitated solidis filtered off with suction and rinsed with methanol. The residue isdried at 40° C. in vacuo. Filtration of the crude product through silicagel with heptane/ethyl acetate 1:1 gives 26 g (75% of theory).

The following brominated compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

72%

80%

77%

CH₃MgBr

72%

Bisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine(7-1)

25 g (50 mmol) of 7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol aredissolved in 300 ml of dried THF in a flask which has been dried byheating. The solution is saturated with N₂. The clear solution is cooledto 5° C., and 20 ml (150 mmol) of triethylamine, 122 mg of4-dimethylaminopyridine and 8.65 ml of trifluoromethanesulfonicanhydride are then added. The reaction mixture is slowly warmed to roomtemperature. The reaction mixture is subsequently diluted with heptane,evaporated in a rotary evaporator and partitioned with water, and theorganic phase is washed three times with water, dried over Na₂SO₄ andevaporated in a rotary evaporator. Filtration of the crude productthrough silica gel with heptane/ethyl acetate 1:1 gives 30 g (98% oftheory).

18.9 g of the triflate (30 mmol) and 8.16 g of bis-4-biphenylamine (25mmol) are dissolved in 240 ml of toluene: the solution is degassed andsaturated with N₂. 0.74 g (1.79 mmol) of S-Phos and 1.36 g of palladiumdba (1.49 mmol) are then added. 5.7 g of sodium tert-butoxide (59.7mmol) are subsequently added. The reaction mixture is heated at 85° C.for 3 h under a protective atmosphere. The mixture is subsequentlypartitioned between toluene and water, and the organic phase is washedthree times with water, dried over Na₂SO₄ and evaporated in a rotaryevaporator. After filtration of the crude product through silica gelwith toluene, the residue which remains is recrystallised fromheptane/toluene. The purity is 99.9%. The yield is 15 g (65% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

73%

80%

69%

75%

Example 8 Synthesis of the compoundN*2*,N*5*,N*5*-trisbiphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H-fluorene-2,5-diamine(8-1)

8-(Biphenyl-4-ylbiphenyl-2-ylamino)benzo[c]chromen-6-one

19.0 g of biphenyl-2-ylbiphenyl-4-ylamine (59 mmol) and 16.3 g of8-bromobenzo[c]chromen-6-one (59 mmol) are dissolved in 400 ml oftoluene: the solution is degassed and saturated with N₂. 2.36 ml (2.36mmol) of a 1 M tri-tert-butylphosphine solution and 0.27 g (1.18 mmol)of palladium(II) acetate are then added. 11.6 g of sodium tert-butoxide(109 mmol) are subsequently added. The reaction mixture is heated at theboil for 3 h under a protective atmosphere. The mixture is subsequentlypartitioned between toluene and water, and the organic phase is washedthree times with water, dried over Na₂SO₄ and evaporated in a rotaryevaporator. After filtration of the crude product through silica gelwith toluene, the residue which remains is recrystallised fromheptane/toluene. The yield is 27 g (90% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

85%

75%

7-(Biphenyl-4-ylbiphenyl-2-ylamino)-9,9-diphenyl-9H-fluoren-4-ol

The following compounds are prepared analogously to7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-ol:

Starting Starting material 1 material 2 Product Yield

88%

73%

CH₃MgBr

76%

N*2*,N*5*,N*5*-Trisbiphenyl-4-yl-N*2*-biphenyl-2-yl-9,9-diphenyl-9H-fluorene-2,5-diamine(8-1)

Compound (8-1) is prepared analogously tobisbiphenyl-4-yl-(7-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-4-yl)amine(compound (7-1)):

Starting Starting material 1 material 2 Product Yield

74%

Example 9 Synthesis of the compoundbisbiphenyl-4-yl-(4-dibenzofuran-4-yl-9,9-diphenyl-9H-fluoren-1-yl)amine(9-1) and compounds (9-2) and (9-3)

24.4 g (37 mmol) of1-(bisbiphenyl-4-ylamino)-9,9-diphenyl-9H-fluoren-4-ol are dissolved in210 ml of dried THF in a flask which has been dried by heating. Thesolution is saturated with N₂. The clear solution is cooled to 5° C.,and 15.5 ml (112 mmol) of triethylamine, 100 mg of4-dimethylaminopyridine and 6.45 ml of trifluoromethanesulfonicanhydride are then added. The reaction mixture is slowly warmed to roomtemperature. The reaction mixture is subsequently diluted with heptane,evaporated in a rotary evaporator and partitioned with water, and theorganic phase is washed three times with water, dried over Na₂SO₄ andevaporated in a rotary evaporator. Filtration of the crude productthrough silica gel with heptane/ethyl acetate 1:1 gives 26.7 g (91% oftheory).

17.2 g (22 mmol) of1-(bisbiphenyl-4-ylamino)-9,9-diphenyl-9H-fluoren-4-ol, 6.9 g (33 mmol)of 4-bibenzofuranboronic acid, 9.0 g of sodium metaborate octahydrate(32.9 mmol) and 0.03 ml of hydrazinium hydroxide (0.657 mmol) aresuspended in 200 ml of THF. 0.3 g (0.44 mmol) ofbis(triphenyl-phosphine)palladium dichloride is added to thissuspension, and the reaction mixture is heated at 70° C. for 18 h. Aftercooling, the mixture is partitioned between ethyl acetate and water, andthe organic phase is washed three times with water, dried over Na₂SO₄and subsequently evaporated to dryness. After filtration of the crudeproduct through silica gel with toluene, the residue which remains isrecrystallised from heptane/toluene and subsequently sublimed. The yieldis 12 g (70% of theory).

The following compounds are prepared analogously:

Starting Starting material 1 material 2 Product Yield

74%

73%

76%

Example 10 Characterisation of the Compounds

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

The data for various OLEDs are shown in the following examples V1 to V13and E1 to E43 (see Tables 1, 3 and 2, 4). The substrates used are glassplates which have been coated with structured ITO (indium tin oxide) ina thickness of 50 nm. The OLEDs basically have the following layerstructure: substrate/optional hole-injection layer (HIL1)/hole-transportlayer (HTL)/hole-injection layer (HIL2)/electron-blocking layer(EBL)/emission layer (EML)/electron-transport layer (ETL)/optionalelectron-injection layer (EIL) and finally a cathode. The cathode isformed by an aluminium layer with a thickness of 100 nm. The precisestructure of the OLEDs is shown in Tables 1 and 3. The materialsrequired for the production of the OLEDs are disclosed above.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter) with which thematrix material or matrix materials is (are) admixed in a certainproportion by volume by co-evaporation. An expression such as H1:SEB1(95%:5%) here means that material H1 is present in the layer in aproportion by volume of 95% and SEB1 is present in the layer in aproportion of 5%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in lm/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines) assuming Lambert emissioncharacteristics, and the lifetime are determined. Theelectroluminescence spectra are determined at aluminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The expression EQE @ 1000 cd/m² denotes the external quantumefficiency at an operating luminous density of 1000 cd/m². LT80 @ 6000cd/m² is the lifetime by which the OLED has dropped from a luminance of6000 cd/m² to 80% of the initial intensity, i.e. to 4800 cd/m². The datafor the various OLEDs are summarised in Tables 2 and 4.

Use of Compounds According to the Invention as Hole-Transport Materialsin OLEDs

In particular, compounds according to the invention are suitable as HIL,HTL or EBL in OLEDs. They are suitable as a single layer, but also asmixed component as HIL, HTL, EBL or within the EML.

Compared with NPB reference components (V1, V8), the samples comprisingthe compounds according to the invention exhibit both higherefficiencies and also significantly improved lifetimes, both in singletblue and also in triplet green.

Compared with reference material HTMV1 (V2, V9), compound (1-1)according to the invention (E1, E7) has significantly better lifetimesin blue and green.

Compared with reference materials HTMV2-HTMV6 (V3-V7 and V9-V13),materials (1-1), (1-4), (1-7), (5-1), (4-1), (1-12), (1-13), (1-14),(1-15), (1-3), (6-3), (6-2), (6-1), (6-4), (6-5), (8-1), (7-1), (7-2),(9-2), (2-7), (2-8), (2-9), (2-10) and (1-17) according to the inventionexhibit better lifetimes in blue and/or green.

Use of Compounds According to the Invention as Hole-Transport Materialsin Fluorescent and Phosphorescent OLEDs

In particular, compounds according to the invention are suitable as HIL,HTL or EBL in OLEDs. They are suitable as a single layer, but also asmixed component as HIL, HTL, EBL or within the EML.

Compared with NPB reference components (V1), all samples comprising thecompounds according to the invention exhibit both higher efficienciesand also significantly improved lifetimes in singlet blue and tripletgreen.

TABLE 1 Structure of the OLEDs (layer structure:substrate/HIL1/HTL/HIL2/EBL/EML/ETL/EIL(1 nm LiQ)/cathode) HIL1 HTL HIL2EBL EML ETL Thickness/ Thickness/ Thickness/ Thickness/ Thickness/Thickness/ Ex. nm nm nm nm nm nm V1 HIL1 HIL2 HIL1 NPB H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V2 HIL1 HIL2 HIL1HTMV1 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm V3 HIL1 HIL2 HIL1 HTMV2 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm V4 HIL1 HIL2 HIL1 HTMV3 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm V5 HIL1 HIL2 HIL1HTMV4 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm V6 HIL1 HIL2 HIL1 HTMV5 H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm V7 HIL1 HIL2 HIL1 HTMV6 H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E1 HIL1 HIL2 HIL1(1-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E2 HIL1 HIL2 HIL1 (1-4) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E3 HIL1 HIL2 HIL1 (1-7) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E4 HIL1 HIL2 HIL1(5-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E5 HIL1 HIL2 HIL1 (4-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E6 HIL1 HIL2 HIL1  (1-12) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E7 HIL1 HIL2 HIL1 (1-13) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E8 HIL1 HIL2 HIL1  (1-14) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E9 HIL1 HIL2 HIL1  (1-15) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E10 HIL1 HIL2 HIL1(6-3) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E11 HIL1 HIL2 HIL1 (6-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E12 HIL1 HIL2 HIL1 (6-1) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E13 HIL1 HIL2 HIL1(6-4) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E14 HIL1 HIL2 HIL1 (6-5) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E15 HIL1 HIL2 HIL1 (8-1) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E16 HIL1 HIL2 HIL1(7-1) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E17 HIL1 HIL2 HIL1 (7-2) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E18 HIL1 HIL2 HIL1 (9-2) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm E19 HIL1 HIL2 HIL1(2-7) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm30 nm E20 HIL1 HIL2 HIL1 (2-8) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm140 nm 5 nm 20 nm 20 nm 30 nm E21 HIL1 HIL2 HIL1  (2-10)H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nmE22 HIL1 HIL2 HIL1 (2-9) H1(95%):SEB1(5%) ETM1(50%):LiQ(50%) 5 nm 140 nm5 nm 20 nm 20 nm 30 nm E23 HIL1 HIL2 HIL1  (1-17) H1(95%):SEB1(5%)ETM1(50%):LiQ(50%) 5 nm 140 nm 5 nm 20 nm 20 nm 30 nm

TABLE 2 Data for the OLEDs EQE @ LT80 @ 1000 cd/m² 6000 cd/m² CIE Ex. %[h] X y V1 4.8 70 0.14 0.17 V2 6.8 160 0.14 0.14 V3 6.9 115 0.14 0.14 V46.8 115 0.14 0.14 V5 6.5 130 0.14 0.15 V6 6.6 100 0.14 0.14 V7 6.9 1350.13 0.14 E1 7.0 180 0.14 0.15 E2 6.9 175 0.13 0.15 E3 7.0 165 0.13 0.15E4 6.7 150 0.14 0.15 E5 6.9 170 0.14 0.13 E6 7.0 145 0.14 0.14 E7 7.0155 0.14 0.14 E8 7.8 120 0.14 0.14 E9 6.9 135 0.13 0.14 E10 6.9 150 0.140.14 E11 7.0 135 0.14 0.13 E12 7.0 180 0.14 0.15 E13 7.0 150 0.14 0.14E14 7.2 170 0.14 0.14 E15 7.0 150 0.14 0.14 E16 6.9 160 0.14 0.14 E176.9 155 0.14 0.15 E18 6.9 170 0.14 0.14 E19 6.9 135 0.14 0.14 E20 7.0115 0.14 0.14 E21 7.0 150 0.14 0.14 E22 7.0 135 0.14 0.14 E23 7.0 1400.14 0.14

TABLE 3 Structure of the OLEDs (layerstructure:substrate/HTL/HIL2/EBL/EML/ETL/cathode) HTL HIL2 EBL EML ETLThickness/ Thickness/ Thickness/ Thickness/ Thickness/ Ex. nm nm nm nmnm V8 HIL2 HIL1 NPB H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20nm 30 nm 40 nm V9 HIL2 HIL1 HTMV1 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%)70 nm 5 nm 20 nm 30 nm 40 nm V10 HIL2 HIL1 HTMV2 H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V11 HIL2 HIL1 HTMV3H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm V12HIL2 HIL1 HTMV5 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30nm 40 nm V13 HIL2 HIL1 HTMV6 H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 20 nm 30 nm 40 nm E24 HIL2 HIL1 (1-1) H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E25 HIL2 HIL1 (1-4)H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E26HIL2 HIL1 (1-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30nm 40 nm E27 HIL2 HIL1 (5-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 20 nm 30 nm 40 nm E28 HIL2 HIL1 (4-1) H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E29 HIL2 HIL1 (1-12)H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E30HIL2 HIL1 (1-13) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm30 nm 40 nm E31 HIL2 HIL1 (1-14) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70nm 5 nm 20 nm 30 nm 40 nm E32 HIL2 HIL1 (1-3) H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E33 HIL2 HIL1 (1-15)H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E34HIL2 HIL1 (6-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30nm 40 nm E35 HIL2 HIL1 (6-1) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 20 nm 30 nm 40 nm E36 HIL2 HIL1 (6-4) H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E37 HIL2 HIL1 (7-2)H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E38HIL2 HIL1 (9-2) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30nm 40 nm E39 HIL2 HIL1 (2-7) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 20 nm 30 nm 40 nm E40 HIL2 HIL1 (2-8) H2(88%):Irpy(12%)ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E41 HIL2 HIL1 (2-10)H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30 nm 40 nm E42HIL2 HIL1 (2-9) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm 5 nm 20 nm 30nm 40 nm E43 HIL2 HIL1 (1-17) H2(88%):Irpy(12%) ETM1(50%):LiQ(50%) 70 nm5 nm 20 nm 30 nm 40 nm

TABLE 4 Data for the OLEDs Efficiency @ LT80 @ 1000 cd/m² 8000 cd/m² CIEEx. % [h] x Y V8 13.4 85 0.36 0.61 V9 16.3 140 0.35 0.62 V10 16.0 1300.36 0.61 V11 16.7 155 0.36 0.61 V12 16.4 150 0.37 0.60 V13 17.0 1700.35 0.62 E24 17.2 210 0.35 0.61 E25 17.2 200 0.36 0.61 E26 17.5 1900.36 0.61 E27 16.7 190 0.37 0.60 E28 17.4 200 0.35 0.61 E29 17.0 1800.37 0.61 E30 17.0 180 0.37 0.61 E31 17.5 220 0.37 0.61 E32 17.3 1700.37 0.61 E33 17.2 200 0.37 0.61 E34 17.3 210 0.37 0.61 E35 17.2 2200.37 0.61 E36 17.2 190 0.37 0.61 E37 17.2 200 0.37 0.61 E38 16.9 2200.37 0.61 E39 16.9 160 0.37 0.61 E40 170 170 0.37 0.61 E41 17.0 195 0.370.61 E42 17.0 180 0.37 0.61 E43 17.1 190 0.37 0.61

1.-22. (canceled)
 23. A compound of the general formula (1)

where the following applies to the symbols and indices used: R¹ is oneach occurrence, identically or differently, H, D, F, Cl, Br, I,C(═O)R⁴, CN, Si(R⁴)₃, NO₂, P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁴ and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, C═S, C═NR⁴,—C(═O)O—, —C(═O)NR⁴—, P(═O)(R⁴), —O—, —S—, SO or SO₂ and where one ormore H atoms in the above-mentioned groups is optionally replaced by D,F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 6 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁴, or an aryloxy group having 5 to60 aromatic ring atoms, which is optionally substituted by one or moreradicals R⁴, or an aralkyl group having 5 to 60 aromatic ring atoms,which may in each case be substituted by one or more radicals R⁴, wherethe two radicals R¹ is optionally linked to one another and may form aring, so that a spiro compound forms in position 9 of the fluorene,where spirobifluorenes are excluded; R² and R³ are on each occurrence,identically or differently, preferably identically, H, D, F, Cl, Br, I,C(═O)R⁴, CN, Si(R⁴)₃, NO₂, P(═O)(R⁴)₂, S(═O)R⁴, S(═O)₂R⁴, N(R⁴)₂, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 20 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 20C atoms or an alkenyl or alkynyl group having 2 to 20 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁴ and where one or more CH₂ groups in the above-mentioned groups isoptionally replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, C═S, C═NR⁴,—C(═O)O—, —C(═O)NR⁴—, P(═O)(R⁴), —O—, —S—, SO or SO₂ and where one ormore H atoms in the above-mentioned groups is optionally replaced by D,F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring systemhaving 6 to 30 aromatic ring atoms, which may in each case besubstituted by one or more radicals R⁴, or an aryloxy group having 5 to60 aromatic ring atoms, which is optionally substituted by one or moreradicals R⁴, or an aralkyl group having 5 to 60 aromatic ring atoms,which may in each case be substituted by one or more radicals R⁴, wheretwo or more radicals R² or two or more radicals R³ is optionally linkedto one another and may form a ring; R⁴ is on each occurrence,identically or differently, H, D, F, Cl, Br, I, C(═O)R⁵, CN, Si(R⁵)₃,NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, N(R⁵)₂, a straight-chain alkyl,alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclicalkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl oralkynyl group having 2 to 20 C atoms, where the above-mentioned groupsmay each be substituted by one or more radicals R⁵ and where one or moreCH₂ groups in the above-mentioned groups is optionally replaced by—R⁵C═CR⁵—, —C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR⁵—,P(═O)(R⁵), —O—, —S—, SO or SO₂ and where one or more H atoms in theabove-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system having 5 to 30aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁵, or an aryloxy or heteroaryloxy group having 5 to 30aromatic ring atoms, which is optionally substituted by one or moreradicals R⁵; R⁵ is selected from the group consisting of H, D, F, analiphatic hydrocarbon radical having 1 to 20 C atoms or an aromatic orheteroaromatic ring system having 5 to 30 C atoms, in which one or moreH atoms is optionally replaced by D or F, where two or more adjacentsubstituents R⁵ may form a mono- or polycyclic, aliphatic ring systemwith one another; q is 1, and p and r are 0; Z^(a) ₀, Z^(c) ₀ are R³;Z^(b) ₁ is

B′ is an aryl group having 6 to 30 ring atoms or a mono- or bicyclicheteroaryl group having 5 to 30 ring atoms, each of which is optionallysubstituted by one or more radicals R⁴; Ar¹, Ar² are on each occurrence,identically or differently, an aromatic radical having 10 to 60 aromaticring atoms, which may be substituted by one or more radicals R⁶, whichare identical to or different from one another, where the two groups Ar¹or Ar² each contain at least two or more aromatic rings, R⁶ is on eachoccurrence, identically or differently, H, D, F, Cl, Br, I, C(═O)R⁵, CN,Si(R⁵)₃, NO₂, P(═O)(R⁵)₂, S(═O)R⁵, S(═O)₂R⁵, a straight-chain alkyl,alkoxy or thioalkyl group having 1 to 20 C atoms or a branched or cyclicalkyl, alkoxy or thioalkyl group having 3 to 20 C atoms or an alkenyl oralkynyl group having 2 to 20 C atoms, where the above-mentioned groupsmay each be substituted by one or more radicals R⁵ and where one or moreCH₂ groups in the above-mentioned groups is optionally replaced by—R⁵C═CR⁵—, —C≡C—, Si(R⁵)₂, C═O, C═S, C═NR⁵, —C(═O)O—, —C(═O)NR—,P(═O)(R⁵), —O—, —S—, SO or SO₂ and where one or more H atoms in theabove-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system having 5 to 30aromatic ring atoms, which may in each case be substituted by one ormore radicals R⁵, or an aryloxy or heteroaryloxy group having 5 to 30aromatic ring atoms, which is optionally substituted by one or moreradicals R⁵; with the proviso that Z^(a) ₁, Z^(b) ₁ and Z^(c) ₁ in thecompound of the formula (1) contain no fluorene or carbazole groups. 24.The compound according to claim 23, wherein Ar¹ is selected from thefollowing groups of the formulae (37) to (75), optionally substituted byone or more radicals R⁶


25. The compound according to claim 23, wherein Ar² is selected from thefollowing groups of the formulae (37) to (75), which may be substitutedby one or more radicals R⁶


25. The compound according to claim 23, wherein the compound has thegeneral formula (2)

where the definitions from claim 23 apply to the symbols used.
 26. Thecompound according to claim 23, wherein the compound has the generalformula (4)

where the definitions from claim 23 apply to the symbols used.
 27. Thecompound according to claim 23, wherein the two R¹ are identical. 28.The compound according to claim 23, wherein B′ is a phenylene,biphenylene, terphenylene, naphthylene, pyridinylene, pyrimidinylene,pyrazinylene, pyridazinylene, triazinylene, dibenzofuranylene ordibenzothiophenylene group, which is optionally substituted by one ormore radicals R⁴.
 29. The compound according to claim 23, wherein B′ isa phenylene, biphenylene, terphenylene, naphthylene, dibenzofuranyleneor dibenzothiophenylene group, which is optionally substituted by one ormore radicals R⁴.
 30. The compound according to claim 23, wherein B′ isa phenylene, biphenylene or terphenylene group, which is optionallysubstituted by one or more radicals R⁴.
 31. The compound according toclaim 23, wherein B′ is a phenylene group, which is optionallysubstituted by one or more radicals R⁴.
 32. The compound according toclaim 23, wherein B′ is an unsubstituted phenylene group.
 33. Thecompound according to claim 23, wherein B′ is a single bond.
 34. Thecompound according to claim 23, wherein the compound is a monoaminecompound.
 35. A process for the preparation of the compound according toclaim 23 by means of one-step Buchwald coupling by reacting a fluorenederivative which contains a leaving group with Ar²—NH—Ar¹.
 36. A processfor the preparation of the compound according to claim 23 by means oftwo-step Buchwald coupling by stepwise reacting a fluorene derivativewhich contains a leaving group with (1) Ar²—NH₂ and (2) NH₂—Ar¹.
 37. Aprocess for the preparation of the compound according to claim 23,wherein the compound is prepared from a benzochromen-6-one.
 38. Theprocess according to claim 38, comprising the following steps: a) addingan organometallic compound onto a benzochromen-6-one and subsequent b)acid-catalysed cyclisation to give a 4-hydroxyfluorene derivative andsubsequent c) converting the hydroxyl group in position 4 of thefluorene into a leaving group and subsequent d) converting the fluoreneinto the desired product.
 39. An oligomer, polymer or dendrimercontaining one or more compounds according to claim 23, where thebond(s) to the polymer, oligomer or dendrimer is optionally localised atany position in formula (1) that are substituted by R¹ to R⁶.
 40. Acomposition comprising one or more compounds according to claim 23 andat least one further organically functional material selected from thegroup consisting of fluorescent emitters, phosphorescent emitters, hostmaterials, matrix materials, electron-transport materials,electron-injection materials, hole-conductor materials, hole-injectionmaterials, electron-blocking materials and hole-blocking materials. 41.A formulation comprising at least one compound according to claim 23 andat least one solvent.
 42. An electronic device comprising at least onecompound according to claim
 23. 43. The electronic device according toclaim 43, wherein the device is selected from the group consisting oforganic integrated circuits (O-ICs), organic field-effect transistors(O-FETs), organic thin-film transistors (O-TFTs), organic light-emittingtransistors (O-LETs), organic solar cells (O-SCs), organic opticaldetectors, organic photoreceptors, organic field-quench devices(O-FQDs), light-emitting electrochemical cells (LECs), organic laserdiodes (O-lasers) and organic electroluminescent devices (OLEDs).
 44. Anorganic electroluminescent device which comprises the compound accordingto claim 23 is employed in one or more of the following functions: ashole-transport material in a hole-transport or hole-injection layer, asmatrix material in an emitting layer, as electron-blocking material oras exciton-blocking material.